Method and apparatus for producing carbride products

ABSTRACT

A method and apparatus are provided for producing a product comprising a carbide compound, such as for example silicon carbide. A reactor is provided which has a chamber defined therein which is divided into a combustion zone and a reaction zone. A combustible mixture is injected into the combustion zone in a direction generally toward the reaction zone, and is accordingly combusted in the combustion zone. At least one reactant (i.e. silane) is injected at the boundary between the zones into the reactor chamber in a direction generally parallel to the longitudinal axis of the chamber so as to react to form raw product comprising the carbide compound.

BACKGROUND OF THE INVENTION

This invention relates to a method and apparatus for producing carbideproducts, such as silicon carbide.

Various carbide powders, such as silicon carbide, are useful as advancedceramic materials in the fabrication of highly stressed, wear resistantceramic parts, such as those employed in heat engines, turbo-chargerrotors and heat exchangers. Although synthesis techniques such as thoseinvolving plasma and laser heating of gaseous reactants havesuccessfully produced submicron carbide powders, it would be desirableto synthesize sinterable carbide products in a manner better suited toeconomical, large scale synthesis. In this regard, it is particularlyadvantageous to minimize the formation of deposits on walls of a carbidereactor so as to thereby minimize down-time for removing such deposits.

SUMMARY OF THE INVENTION

It is, therefore, an object of the invention to provide a method andapparatus which are economical in producing carbide products in areactor and which minimize reactor wall deposits so as to be well suitedto large scale synthesis.

The above object is realized by a method which comprises: providing areactor having a chamber defined therein which has a longitudinal axisand longitudinally separated upstream and downstream ends, wherein thechamber comprises a combustion zone and a reaction zone such that thecombustion zone longitudinally extends from the upstream end to asurface boundary between the zones and such that the reaction zonelongitudinally extends from the surface boundary to the downstream end;establishing a flow of a combustible mixture in the combustion zone soas to generally flow in a direction toward the reaction zone, whereinthe combustible mixture comprises a mixture of a fuel and an oxidant;combusting the combustible mixture in the combustion zone to produce hotcombustion products which flow toward and into the reaction zone;injecting at least one reactant into the reactor chamber from at leastone outlet of at least one reactant nozzle such that the reactant(s)exits the reactant nozzle outlet(s) at the surface boundary in adirection generally parallel to the longitudinal axis, whereintemperature conditions in at least a portion of the reaction zone are atleast about 1400° C. and wherein the elemental molar ratio of carbon tooxygen for the combination of the combustible mixture and thereactant(s) is at least about 0.8:1, and further wherein the reactant(s)is capable of reacting in the reaction zone to form a carbide compound;whereby a product powder comprising the carbide compound is produced inthe reaction zone.

According to another aspect of the invention, there is provided anapparatus which comprises: a reactor as described above; means forinjecting a combustible mixture into the combustion zone which comprisesat least one combustion nozzle having at least one outlet whichcommunicates with the combustion zone and which is adapted to releasecombustible mixture into the combustion zone in a direction generallytoward the reaction zone; and means for injecting at least one reactantinto the reaction zone which comprises at least one reactant nozzlehaving at least one outlet which communicates with the chamber at thesurface boundary and which is adapted to release the reactant(s) intothe reactor chamber in a direction generally parallel to thelongitudinal axis of the chamber, wherein the reactant(s) is capable ofreacting in the chamber to form a carbide product.

According to preferred embodiments of the invention described herein, aplurality of combustion nozzle outlets define at least one linearboundary whose projection in a direction generally parallel to thelongitudinal axis of the chamber and onto the above-mentioned surfaceboundary generally surrounds a reaction nozzle outlet. It is alsopreferred that the reaction nozzle have an outlet which is positionedsubstantially on the longitudinal axis of the chamber.

The method and apparatus of the invention are economical in requiringthe use of inexpensive combustible fuels as the heating source and inrequiring a minimal investment for construction of the reactor.Moreover, it has been found that injecting the reactants in a directiongenerally parallel to the longitudinal axis of the chamber isparticularly effective at minimizing deposits on the reactor chamberwalls. The preferred relative positioning of the combustion and reactantnozzles as discussed above particularly enhance this desired effect.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a reactor in accordance with oneembodiment of the invention.

FIG. 2 is a cross-sectional view of the embodiment of FIG. 1 as viewedalong line 2--2.

FIGS. 3 and 4 are enlarged cross-sectional views of nozzles which areshown in FIG. 1.

FIG. 5 is a cross-sectional view of a reactor in accordance with anotherembodiment of the invention.

FIG. 6 is a cross-sectional view of the embodiment of FIG. 5 as viewedalong line 6--6.

FIG. 7 is an enlarged cross-sectional view of a reactant nozzle which isshown in FIG. 5.

DETAILED DESCRIPTION OF THE INVENTION

Referring to FIG. 1, there is shown a cross-sectional view of a reactor10 having defined therein a chamber 12 which has a longitudinal axis 14and longitudinally separated upstream and downstream ends 16 and 18,respectively. Chamber 12 includes a combustion zone 12a and a reactionzone 12b situated such that combustion zone 12a extends from upstreamend 16 to an imaginary surface, in this case planar, boundary 20 betweenthe zones and such that the reaction zone 12b extends from boundary 20to downstream end 18.

Chamber 12 is defined by refractory tubes 22 and 24 and also inserts26a, b and c. Such tubes and inserts are preferably composed of arefractory material resistant to temperatures of at least 2000° C., suchas zirconia, which is commercially available from Zircoa Products ofSolon, Ohio.

As shown, there is provided several additional coaxially positionedlayers of refractory material which are generally annular in shape andwhich surround tubes 22 and 24, including: layer 28, preferablycomprising zirconia powder insulation, available from Zircar Products ofFlorida, N.Y., which allows for contraction and expansion of this layer;layer 30, which preferably comprises alumina-silica blanket insulation,commercially available under the trademark Fiberfrax® from Carborundumof Niagara Falls, N.Y.; and layer 32, which may be of the samecomposition as layer 30. A refractory cyclinder 34, preferably lowdensity thermal insulating alumina available from Zircar Products ofFlorida, N.Y., is illustrated as separating layers 28 and 30, and ametal cylinder 36 most preferably composed of stainless steel separateslayers 30 and 32. Cylinders 34 and 36 assist in providing structuralsupport for the reactor.

The outermost refractory layer 32 is held in place by a cloth material42, such as fiberglass, which wraps around the exterior surface of layer32. The bottom end of the various layers are supported by a metal plate44. The reactor is preferably oriented vertically as shown for the sakeof operating convenience. If any of the refractory material breaks orcracks it tends to stay in position if the various layers and tubes arevertically positioned. Therefore, operation can sometimes continuedespite such structural defects. Other reactor orientations are withinthe scope of the invention, however.

Each of combustion nozzles 46a and 46b are connected to a source of fueland oxidant and have respective outlet ends 48a and 48b whichcommunicate with combustion zone 12a of chamber 12 at a position closelyadjacent to upstream end 16 of chamber 12. As shown, nozzles 46a and 46bare surrounded by refractory inserts 52 positioned near upstream end 16.Although not shown in FIG. 1, a third combustion nozzle 46c having anassociated outlet end 48c is also provided. See FIG. 2 which shows allthree combustion nozzles.

A single reactant nozzle 54 is connected to a source of reactants,discussed later in detail, and extends through refractory inserts 52 andfrom upstream end 16 of chamber 12 to an outlet end 56 whichcommunicates with chamber 12 at surface boundary 20. As shown, nozzle 54has a longitudinal axis 57 which in the illustrated embodiment isparallel to longitudinal axis 14 of chamber 12. Most preferably for thepurpose of optimally minimizing deposits on chamber-defining walls(hereinafter simply referred to as chamber walls) of, for example,refractory tubes 24 and 26, etc., longitudinal axis 57 corresponds tolongitudinal axis 14 of chamber 12 such that said outlet 56 ispositioned substantially on longitudinal axis 14. A plurality ofgenerally annular refractory members 58, preferably composed of asuitable temperature resistant material such as zirconia-based ZYFB3 asavailable from Zircar Products, are preferably stacked upon one anotherso as to surround nozzle 54 along its length within chamber 12. Otherthermal insulating layers and coatings are within the scope of theinvention. Such refractory members 58 minimize heat exchange betweennozzle 54 and chamber 12 so as to thereby minimize heat loss from thechamber.

Proper positioning of the nozzles with respect to each other is animportant consideration in optimizing operating efficiency and qualityof the product. It is desirable, for example, to position reactionnozzle outlet 56 and corresponding surface boundary 20 far enoughdownstream from the combustion nozzle outlets so that substantially allof the free oxygen has reacted with the fuel to form combustion productsbefore reaching the surface boundary 20. Such positioning of the nozzlesmeans that there is substantially no free oxygen (0₂ in its free gaseousstate, uncombined with any other component) at surface boundary 20, thusavoiding the undesirable oxidation of one of the reactants, as will bediscussed further in connection with operation of the apparatus. It isfurthermore desirable to position outlet 56 sufficiently downstream toavoid the jet pump effect on gases flowing from outlet 56. This effecttends to pull the reactants upstream rather than the intended downstreamflow. However, in addition to the above considerations, outlet 56 shouldbe positioned sufficiently upstream to ensure that temperatures to whichthe reactants are exposed are conducive to the formation of carbideproduct. In regard to the above-discussed optimum positioning ofreaction nozzle outlet 56, the illustrated embodiment enablesparticularly convenient adjustment of the position of outlet 56 bysimply longitudinally withdrawing or further extending nozzle 54 from orinto chamber 12.

Also shown in FIG. 1 is conduit 60 which is connected at one end toreactor 10 so as to communicate with the downstream end 18 of chamber12. Conduit 60 receives carbide product powder therethrough which thenpasses to a suitable collector, discussed further below. Conduit 60 inthe illustrated embodiment not only functions to transport the productto the collector, but also functions as a heat exchanger. The outside ofconduit 60 is exposed to a cooling means such as ambient air whichallows heat transfer via both natural convection and radiation. Suchheat transfer effects cooling of the product powder as it flows throughconduit 60, which is highly desirable in order to prevent undesirablereactions involving, for example, oxidation of the carbide product toform unwanted oxides. In addition, such cooling of the product powder isdesirable to prevent damage to the collector from excessively hotproduct. In instances where a cloth filter bag is used as the collector,conduit 60 should be of sufficient length to cool the product powder toa desired temperature, typically below about 100° C., before it entersthe collector. Other types of collectors require less cooling. Ifdesired, the cooling effect can be further enhanced by surroundingconduit 60 with a cooling coil or jacket having coolant fluid flowingtherethrough.

With respect to materials for conduit 60, it is preferable that anon-metallic material be employed which will not add any undesirablemetal contaminants to the product. If the desired product is siliconcarbide for example, quartz (silicon dioxide) is preferred sincemolecular structures characterized by silicon-oxygen bonds are alreadypresent in the reactor product such that essentially no additionalcontaminants will enter the product stream. Quartz is also aparticularly preferred material because of its high emissivity andexcellent thermal shock resistance. However, other heat exchangematerials, including metals, are within the scope of certain aspects ofthe invention.

The collector can be any suitable means of collecting the productpowder. One suitable collector, as discussed above, comprises a clothfilter bag connected to the downstream end of conduit 60. Other suitablecollectors include metal filters, electrostatic precipitators andcyclone separators. Of course, regardless of what type of collector isused a pressure differential should preferably be established, by asuitable pump, across the collector to draw the product powder throughconduit 60 and into the collector.

Referring now to FIG. 2, this view shows all three combustion nozzleoutlets 48a, 48b and 48c and their relative positions with respect toreaction nozzle outlet 56. As can be seen from FIGS. 1 and 2, thecombustion nozzle outlets define an imaginary linear boundary 61 whoseprojection in a direction generally parallel to longitudinal axis 14 ofchamber 12 and onto surface boundary 20 generally surrounds outlet 56.In operation this feature advantageously provides a sheath of combustionproducts around reactants injected from outlet 56 so as to assist inprotecting the chamber walls from deposit-forming reactions involvingthe reactants. As used herein and in the appended claims, the term"linear boundary" is broadly construed to include any boundary definedby a moving point, and is not limited to one or more straight linesegments. In the particular embodiment illustrated, boundary 61 isgenerally triangular in shape and is positioned with respect to outlet56 such that outlet 56 is generally centrally located within theabove-mentioned projection of boundary 61. Most preferably, and asshown, the combustion nozzle outlets are equidistantly spaced from oneanother.

Referring to FIG. 3, there is shown a cross-sectional view of a portionof a nozzle labeled as 46, which represents any one of the combustionnozzles 46a, 46b and 46c which are each identical in structure andoperation. Nozzle 46 comprises a tubular member 62, preferablyconstructed of a metal such as stainless steel, which has an innersidewall 62a and an outer sidewall 62b. Such sidewalls define agenerally annular space 64 therebetween which is connected to a sourceof coolant fluid such as water or ethylene glycol or a combinationthereof, which could also include minor amounts of additives such ascorrosion inhibitors, etc. if desired. A tubular member 66 is positionedwithin annular space 64 so as to generally divide the space intoentrance and exit passageways for the coolant fluid. As shown, coolantfluid flows toward the tip of nozzle 46 as indicated at 68, and flowsaway from the tip in the opposite direction as indicated at 70. Thedirection of coolant fluid flow may be reversed if desired. The flow ofcoolant fluid through space 64 assists in preventing melting of themetallic tubular members, and also assists in preventing the flame fromburning back (flashback) into nozzle 46 by keeping the interior ofnozzle 46 below the autoignition temperature of the fuel/oxidantmixture. The interior of nozzle 46 is connected to a source of fuel andoxidant such that a flow of the fuel/oxidant mixture is establishedthrough nozzle 46 as indicated at 72.

Referring to FIG. 4, there is shown a cross-sectional view of nozzle 54having outlet end 56. Nozzle 54 is preferably constructed of the same orsimilar metallic material as that used for nozzle 46, and includestubular members 74 and 76. As shown, tubular member 74 is positionedgenerally coaxially within tubular member 76 such that a generallyannular space 78 is defined between the interior surface of member 76and the exterior surface of member 74. The interior of tubular member 74is connected to a source of reactants to provide a flow of reactantstherethrough as indicated at 79. Tubular member 76 is generally of thesame design as member 62 in FIG. 2, and includes respective inner andouter sidewalls 76a and 76b between which there is defined a generallyannular space 80. A tubular member 82 is positioned within annular space80 so as to divide it into entrance and exit passageways. Space 80 isconnected to a source of coolant fluid so as to establish respectiveentrance and exit flow paths 84 and 86. The reverse direction of coolantfluid flow can be employed if desired. The flow of coolant fluid notonly assists in preventing melting of the metallic tubular members, butalso helps prevent the formation of carbide deposits within nozzle 54 bymaintaining the temperature of the nozzle below temperature limitsconducive to carbide formation. This avoids the need to periodicallyclean carbide deposits from nozzle surfaces.

Annular space 78 is connected to a purge gas source to establish a flowof such purge gas through annular space 78 in the direction of outletend 56, as indicated at 88. Thus, this flow of purge gas exits outletend 56 in a generally annular stream so as to surround the reactants asthey exit the nozzle. This annular gas stream forms a sheath around thereactants so as to prevent contact of the hot combustion gases inchamber 12 (see FIG. 1) with the reactants immediately after their exitfrom nozzle 54, thereby preventing the formation of carbide deposits onthe tip of nozzle 54. Such deposits, if not prevented, can eventuallylead to blockage of reactant flow from nozzle 54 and consequent reactorshutdown. Of course, the insulative sheath of purge gas disperses afteronly a few milliseconds, but this is sufficient time to allow thereactants to flow far enough away from the nozzle tip to preventformation of undesirable deposits. The choice of purge gas is notcritical, and can be, for example, an inert gas (i.e. helium or argon),a cooled waste gas as discharged from the reactor, or a reactivecarbon-containing gas (i.e. hydrocarbon) which can contribute carbon tothe reactive stream for formation of carbides. If a carbon-containinghydrocarbon is used as the purge gas, it typically will not decomposequickly enough to result in any undesirable carbon deposits on the tipof nozzle 54.

The various gas flows are preferably established and controlled byconventional equipment not shown in the drawings. Gas can be suppliedby, for example, pressurized gas bottles. The gas can pass from such apressurized container and through an orifice plate whose orifice issized to achieve sonic velocity of the gas. Such a sonic velocityprevents pressure disturbances from traveling upstream, so that whateverhappens downstream near the reactor from traveling upstream, so thatwhatever happens downstream near the reactor will not affect the desiredflow rate of gas. A pressure regulator can be employed to control therate of flow of the gas.

Turning now to another aspect of the invention, there is provided amethod of making a carbide compound using the above described apparatus.Reference will be made to the drawings in describing a preferredembodiment of this method.

As used herein and in the appended claims, a carbide compound is definedas a compound of a first elemental component and a second, carboncomponent. Generally speaking, a carbide compound is produced inaccordance with the illustrated embodiment by reacting two reactants.The first reactant contains the first component whereas the secondreactant contains the second, carbon component.

According to certain broad aspects of the invention, the first componentas contained in the first reactant may be any element capable ofcombining with carbon to form a carbide compound. For example, the firstcomponent may be a metal such as tungsten, chromium, titanium,zirconium, molybdenum or iron. Halides of such metals are particularlysuitable as the first reactant. Or, the first component may be ametalloid such as boron or silicon. As stated previously, siliconcarbide is a very useful carbide compound. Ceramic parts can be madefrom silicon carbide powder which have excellent mechanical strength andheat resistance. Therefore, reactants having silicon as the firstcomponent are of particular interest in connection with the presentinvention.

Preferred silicon-containing reactants which are compounds of siliconinclude silane (SiH₄) and substituted silanes. As used herein and in theappended claims, a substituted silane can be generally expressed by theformula SiABCD where each of A, B, C and D can be any element orcombination of elements as long as at least one of A, B, C and D is nothydrogen, and where A, B, C and D can be the same or different. Forexample, any one of A, B, C and D can be selected from hydrogen, ahalogen, an oxygen-containing group (i.e. OSi(CH₃)₃), anitrogen-containing group (i.e. NHSi(CH₃)₃), an alkyl group, an arylgroup, a silyl group, or a group containing multiple silicon atoms.Examples of such substituted silanes include: alkyl silanes such asmethylsilane ((CH₃)SiH₃), dimethylsilane ((CH₃)₂ SiH₂), trimethylsilane((CH₃)₃ SiH) and tetramethylsilane (Si(CH₃)₄); halogenated silanes suchas dichlorosilane (H₂ SiCl₂); halogenated methylsilanes such astrimethyl silicon bromide ((CH₃)₃ SiBr) and dichlorodimethylsilane((CH₃)₂ SiCl₂); siloxanes such as hexamethyldisiloxane ((CH₃)₃SiOSi(CH₃)₃); silazanes such as hexamethyldisilazane ((CH₃)₃SiNHSi(CH₃)₃); and silicon halides such as silicon tetrachloride(SiCl₄). Cyclic and polymeric silicon compounds are also within thescope of the invention. If desired, mixtures of any of the precedingsilicon-containing compounds can be employed. Silane is the presentlypreferred silicon-containing reactant in view of the quality of theproduct.

The second, carbon-containing reactant is preferably a C₁ -C₉ carboncompound such as an alcohol or a hydrocarbon. Suitable alcohols includeethanol and propanol. A hydrocarbon is presently most preferred and canbe selected, by way of example, from the following group: methane,ethane, propane, butane, pentane, hexane, heptane, octane, nonane,ethylene, propylene, acetylene, benzene, toluene, cyclopropane,cyclobutane, cyclopentane, cyclohexane, and mixtures thereof. Althoughsuch C₁ -C₉ carbon compounds are preferred, any carbon-containingreactant capable of reacting with the first reactant to form carbideproducts is within the scope of certain aspects of the invention.

The fuel, which is injected through each of nozzles 46a, 46b and 46c, ispreferably an unsaturated hydrocarbon (having at least one double ortriple bond between carbon atoms), such as, for example, ethylene,propylene, butene, propadiene, butadiene, acetylene, propyne, butyne andmixtures thereof, and can be the same as or different than thehydrocarbon second reactant. A particularly preferred unsaturatedhydrocarbon fuel is a mixture of ethylene and acetylene. Employingacetylene in the fuel has been found to increase the temperature in thereaction zone, discussed further below, as compared to ethylene alone,for example, which is desirable to minimize the oxygen content in theproduct powder and which is further desirable where a reactant such asdichlorodimethylsilane is used which requires a higher temperature thansome other reactants to achieve a desirable reaction rate. Anotherpreferred group of hydrocarbon fuels are cyclic hydrocarbons such ascyclopropane, cyclobutane, and mixtures thereof. Other types of fuels,such as solid fuels substantially comprising pure carbon, and fuelblends are within the scope of certain aspects of the invention as longas the desired temperature conditions and carbon to oxygen ratio, laterdiscussed, are achieved in the reactor.

The oxidant employed should be capable of accepting electrons from thefuel and is preferably an oxygen-containing gas, most preferably pureoxygen. Gaseous mixtures which include oxygen as a single component,such as air, are within the scope of the invention.

In accordance with a preferred procedure for operating the illustratedapparatus, flow of coolant fluid is started with respect to nozzles46a-c and 54, followed by gradual heating of the reactor to normaloperating temperatures. This is done to avoid thermal shock and possiblebreakage to the various refractory materials. One method for thispreheating stage involves initial electrical heating of the refractorylayers with electrical rod heaters (not shown) and heating of chamber 12with a coiled wire electrical heater (not shown) inserted into chamber12, followed by establishment of a combustion flame in combustion zone12a.

In any event, the combustion flame is established in combustion zone 12aby initiating a flow of gaseous fuel through nozzles 46a-c. If thereactor has been preheated electrically, the fuel should spontaneouslyestablish a flame by reacting with ambient air at downstream end 18 ofchamber 12. If the combustion flame does not form, the fuel may beignited with an appropriate ignition device. After the flame isestablished, a flow of air is initiated through nozzles 46a-c so as toproduce a fuel/air mixture. This causes the flame to propagate upstreamso that the flame establishes itself in combustion zone 12a. Propagationof the flame in this manner can be hazardous to an operator implementingthe method such that adequate safety precautions are taken. The reactoris typically operated with this fuel/air mixture for a predeterminedperiod, usually 1/2 hour to 1 hour. Operation of the reactor with air asthe oxidant is part of the preliminary start-up of the reactor togradually heat the reactor.

A flow of pure oxygen is now commenced through nozzles 46a-c to replacethe air. The flow of such oxygen is gradually increased and the flow ofair gradually decreased until a fuel/oxygen combustible mixture isobtained. The combustion flame should be monitored visually throughdownstream end 18 to make sure that the flame does not flash backupstream so as to enter nozzles 46a-c and cause a potentially dangerouscondition. Flashback can be prevented by providing a sufficiently highvelocity of fuel and oxygen exiting each of nozzles 46a-c.

A flow of the fuel/oxygen mixture is thus established in a directiongenerally parallel to axis 14 as indicated at 89, and the fuel andoxygen flow rates are set to be relatively fuel-rich in preparation forcarbide production. The elemental molar ratio of carbon to oxygen forthe fuel/oxygen mixture is preferably at least about 0.7:1, morepreferably in the range of about 0.8:1 to about 1.2:1, and mostpreferably in the range of about 0.9:1 to about 1.1:1. As used herein,the elemental molar ratio of carbon to oxygen means the molar ratio ofcarbon atoms to oxygen atoms. The residence time of the combustiblemixture and hot combustion products formed therefrom in combustion zone12a is typically about 5 to about 20 milliseconds, which is sufficienttime to consume substantially all of the oxygen before reaching boundary20. As discussed previously, this is desirable to avoid the productionof unwanted oxides rather than carbides. Temperature conditions incombustion zone 12a are typically about 1700° C. to about 2000° C. Hotcombustion products produced in combustion zone 12a flow toward and intothe reaction zone 12b as indicated at 90.

The substantially gaseous reactants are now injected into chamber 12from reaction nozzle outlet 56, as indicated at 91, such that thereactants exit outlet 56 at boundary 20 in a direction generallyparallel to the chamber axis 14, preferably generally along chamber axis14 and toward downstream end 18. Such injection of reactants generallyparallel to chamber axis 14 is particularly desirable in minimizingdeposits on the chamber walls. In the illustrated embodiment, the firstand second reactants are premixed to give a desired molar ratio of firstcomponent to carbon in the reactants, typically about 1:2 to about 1:4where silicon is the first component. Such a mixture is passed throughnozzle 54 so as to exit outlet end 56 into chamber 12. If the firstreactant employed is normally a liquid, such first reactant is placed invapor form most conveniently by placing it in a temperature controlledbubbler and passing a purge gas therethrough. The temperature of thecoolant fluid flowing through nozzle 54 can be elevated to the necessaryextent to help prevent condensation of the first reactant as it passesthrough nozzle 54.

Flow rates are adjusted so that the elemental molar ratio of carbon tooxygen for the combination of the reactants and fuel/oxygen mixture isat least about 0.8:1, but is preferably in the range of about 0.9:1 toabout 1.5:1 and most preferably in the range of about 1:1 to about1.3:1. Although the reactions occurring in reaction zone 12b arenumerous and not completely understood, it is believed that the abovecited carbon to oxygen ratios minimize the production of undesirableoxidizing species such as carbon dioxide and water, and produce partialpressures of reducing gases like carbon monoxide and hydrogen which arefavorable to the production of carbides. The preferred carbon to oxygenratios for the fuel/oxygen mixture previously discussed (preferably atleast about 0.7:1, more preferably about 0.8:1 to about 1.2:1, and mostpreferably about 0.9:1 to about 1.1:1) particularly enhance theseconditions favorable to the production of carbides. In addition, reactortemperature is somewhat dependent on the carbon to oxygen ratio, andtemperatures conducive to carbide formation are achievable using theabove-discussed carbon to oxygen ratios.

It is generally preferred to employ a mass ratio of no more than about0.3. As used herein and in the appended claims, the term "mass ratio" isdefined as the ratio of the synthesis rate (i.e. g/min) to the totalmass flow rate (i.e. g/min) of the fuel plus oxidant into combustionzone 12a. The term "synthesis rate" (i.e. g/min) is defined as (m×f)/n,where m represents the molecular weight (i.e. g/gmole) of the carbidecompound, f represents the total molar flow rate (i.e. gmoles/min) offirst component atoms into reaction zone 12b, and n represents thenumber of first component (i.e. silicon) atoms in the carbide compound.The synthesis rate is a theoretical value which is proportional to theflow rate of the first reactant and which assumes 100% reaction of thefirst component atoms to form the carbide compound. Of course, in actualpractice, such 100% conversion does not occur and some losses occur dueto deposit formation on the walls of chamber 12, walls of conduit 60,etc.

If desired, it is within the scope of the invention to inject intochamber 12 in admixture with the reactants a boron-containing compoundwhich will provide boron in the product collected from reaction zone12b. Suitable boron-containing compounds include boranes, such asdiborane (B₂ H₆), other boron hydrides, and boron alkyls. Boron isparticularly useful in the product insofar as it acts as a sintering aidwhen such product is sintered to a ceramic part.

Temperature conditions for at least a portion of reaction zone 12b areat least about 1400° C., preferably in the range of about 1400° C. toabout 1700° C., most preferably in the range of about 1500° C. to about1600° C. The temperature conditions in the reactor can most convenientlybe monitored by means of a thermocouple (not shown) positioned in one ofthe refractory layers. The temperature detected by the thermocouple canbe correlated to actual temperature conditions in the reactor. Ofcourse, a thermocouple can be positioned directly in the chamber 12, butthis requires use of expensive materials such as platinum and/or rhodiumwhich are still subject to deterioration due to the high temperatures inchamber 12.

Pressure conditions in reaction zone 12b are preferably at or nearatmospheric pressure. Other operating pressures are within the scope ofthe invention.

In reaction zone 12b, a product powder is formed from the reactantswhich includes the desired carbide compound and other components as isdiscussed further below. The product powder exits the reactor throughdownstream end 18 and passes into and through conduit 60 to thecollector. After the desired amount of product powder is collected, thereactor is shut down by first switching to air as the oxidant and thengradually decreasing the fuel/oxidant flow rates to provide gradualcooling of the reactor. After shutdown, the reactor is typically allowedto cool for several hours before the supply of coolant fluid to thenozzles is terminated.

Referring now to FIG. 5, there is shown a reactor 110 in accordance withanother embodiment of the invention. The structure of the variousrefractory layers of reactor 110 is substantially similar to that shownin FIG. 1. The combustion nozzles, of which 146a and 146b are shown inFIG. 5, are positioned similarly to that shown in FIGS. 1 and 2 and areof the same structure as that shown in FIG. 3. This embodiment differsfrom the FIG. 1 embodiment with respect to the reactant nozzle 154 whichis received within a refractory tube 155 so as to radially extendthrough the various refractory layers and into chamber 112. As shown,the longitudinal axis 157 of nozzle 154 is generally perpendicular tothe longitudinal axis 114 of chamber 112. Although not visible in FIG.5, nozzle 154 has an outlet indicated at 156 which is positionedsubstantially on chamber axis 114 so as to face downstream end 118 ofchamber 112.

Referring to FIG. 6, combustion nozzle outlets 148a, 148b and 148cdefine a linear boundary 161 and are positioned relative to reactionnozzle outlet 156 of nozzle 154 in a manner similar to that shown inFIG. 2 with respect to combustion nozzle outlets 48a-c and reactionnozzle outlet 56.

Referring to FIG. 7, there is shown a cross-sectional view of reactionnozzle 154. Nozzle 154 includes tubular members 176a and 176b which areoriented similarly to that of inner and outer sidewalls 76a and 76b ofnozzle 54. Coolant fluid flows in the passage defined between tubularmembers 176a and 176b as per entry paths 184 and exit paths 186, andreactants are received through the interior of tubular member 176a asindicated at 179. Nozzle 154 further includes a tip 192 which isconnected to the ends of tubular members 176a and 176b by suitablemeans, such as welds. An L-shaped passage 194 is defined through tip 192so as to extend from a first end communicating with the interior oftubular member 176a to a second end which defines outlet 156.Preferably, tip 192 is composed of a metal such as nickel or copperwhich has a high thermal conductivity, thereby enabling quicktransference of heat from tip 192 to the coolant fluid so as to avoidoverheating and possible melting of the tip. It may be noted that meansis not provided in nozzle 154 for providing a flow of purge gas aroundthe reactants. This feature is omitted in this embodiment solely for thesake of simplicity of construction, and could be provided in nozzle 154if desired.

Operation of the embodiment shown in FIGS. 5-7 is performed in a similarmanner to that procedure described for the embodiment of FIGS. 1-4. Amixture of fuel and oxidant, preferably pure oxygen, is injected fromthe combustion nozzles into combustion zone 112a in a directiongenerally toward reaction zone 112b as indicated at 189. Hot combustionproducts produced in combustion zone 112a flow generally toward and intoreaction zone 112b as indicated at 190. Although the arrows at 190 areshown as straight to indicate the general directional flow of combustionproducts, it should be understood that some turbulence results from flowaround nozzle 154. Finally, reactants exit outlet 156 of reaction nozzle154 at boundary 120 in a direction generally along chamber axis 114 andtoward downstream end 118 as indicated at 191.

In the following description of products produced in accordance with theinvention, it is to be understood that the term "weight percent" asapplied to a component of a composition is based on the total weight ofthe composition.

The product powder as collected directly from the reactor, hereafterdenoted as "raw" powder, is generally black or brown in appearance, andin the case of silicon as the first elemental component, containssilicon carbide, silicon and carbon in addition to that in the siliconcarbide, and oxygen. Such a raw product powder is characterized by thefollowing weight percentages: silicon in the amount of about 30 to about75 weight percent, preferably in the amount of about 50 to about 70weight percent, and most preferably in the amount of about 55 weightpercent to about 70 weight percent; carbon in the amount of about 15 toabout 50 weight percent, preferably in the amount of about 20 to about45 weight percent, and most preferably in the amount of about 30 toabout 40 weight percent; and oxygen in the amount of about 1 to about 30weight percent, preferably in the amount of about 1 to about 20 weightpercent, and most preferably in the amount of about 1 to about 10 weightpercent. Hydrogen can also be present in the raw product in minor butdetectable amounts of between about 0 and about 1 weight percent. NMRanalysis is also taken to indicate that at least some of the siliconatoms in raw product powder are bonded to both carbon and oxygen atoms.In other words, at least some of the silicon in the product issimultaneously bonded to both carbon and oxygen.

The raw product powder in accordance with the invention can be furthercharacterized insofar as a sample of such powder having a relativelyhigh oxygen content in the range of about 3 to about 10 weight percentis sinterable to a sintered ceramic part having a density of at leastabout 2.8 g/cc, or about 85% of the density of pure crystalline siliconcarbide, by a process comprising: pressing the raw product at atemperature of less than about 100° C. to a pressed part having adensity of no more than about 1 g/cc; heating the pressed part to atemperature of about 1700° C. to about 2400° C. without application ofcompaction force so as to produce the sintered part having the densityof at least about 2.8 g/cc; wherein no steps are performed prior to theheating step for removal of any appreciable amounts of oxygen from theraw product or pressed part produced therefrom. As used herein, the term"pressing" refers to any technique for fabricating a self-supportingshape from ceramic particles. Also as used herein, the application of a"compaction force" to a ceramic part means the application of a force tothe part by means of a solid member in contact with the part whichmechanically compacts the part to thereby increase its density.

With respect to particle size, the raw product powder comprisesparticles having diameters in the range of about 0.01 to about 0.3micron.

The raw product powder can be further purified by additional processingto yield a purified product. This purification process typicallyinvolves two stages carried out in a conventional furnace. First, theraw powder is heated in an inert gas (i.e. argon) atmosphere at atemperature of about 1300° C. to about 2400° C., most preferably about1400° C. to about 1800° C., for at least about 15 minutes and mostpreferably in the range of about 1 hour to about 2 hours. This serves toreact molecular structures having silicon-oxygen bonds with carbon tothereby remove oxygen as carbon monoxide and make the silicon availablefor reacting with free carbon to form additional silicon carbide. Incertain instances, the raw powder will have insufficient carbon toremove a substantial portion of the oxygen, thus necessitating theaddition of carbon to the raw powder before heating in the inertatmosphere. Second, the powder resulting from the first purificationstage is heated in an oxygen-containing atmosphere to a temperature ofabout 600° C. to about 900° C., most preferably about 600° C. to about700° C., over a period of at least about 15 minutes and most preferablyfor about 30 minutes to about 2 hours. This stage burns off remainingcarbon in the form of carbon oxides to yield the purified product.

X-ray fluorescence analysis of the purified product indicates that theproduct has less than about 1000 ppm of elemental impurities, whereinsuch elemental impurities include aluminum and those elements of higheratomic numbers, except silicon, up to and including uranium. Mostpreferably, the product has less than about 600 ppm of such impurities.Many impurities undesirably decrease the strength of sintered carbideparts made from product powder.

Individual particles of the purified product in the form of a powder arehighly uniform and have diameters which range from about 0.05 micron toabout 0.50 micron. Submicron and uniform particles are vitalcharacteristics in the production of fine-grained, high strength partsfrom a carbide powder. Crystallite size (size of individual crystals)range from about 30 to about 100 angstroms.

Either the raw or purified product can be sintered into heat resistant,high strength parts in a conventional manner. For example, appropriateamounts of additives such as boron and carbon or yttrium oxide andaluminum oxide can be added to such product, followed by pressing to adesired shape and heating at a temperature of about 1700° C. to about2400° C.

It is to be understood that the above description pertains to preferredembodiments of the invention, but that many variations and modificationsare within the scope of certain aspects of the invention.

For example, although only a single reactant nozzle is provided in theillustrated embodiments, it is within the scope of certain aspects ofthe invention to provide a plurality of reaction nozzles havingrespective outlets which can, by way of example, be positioned aroundthe longitudinal axis of the reactor chamber.

Other variations of the embodiments described above can involvedifferent reactants and/or fuels. For example, it is possible to useexcess carbon from the fuel and/or the first reactant as the source ofcarbon for producing the carbide compound, in which case the second,carbon-containing reactant can be omitted. It is desirable in such anembodiment to utilize a carrier gas, such as nitrogen, helium, argon,hydrogen, carbon monoxide or mixtures thereof in admixture with thefirst reactant to carry the first reactant into the reactor chamber.Since a mixture of carbon monoxide and hydrogen is produced as a wastegas by the reactor, the reactor can serve as a convenient source of suchcarrier gas. Another possible variation could involve employing a fuelwhich includes a preferred unsaturated hydrocarbon as well as amounts ofother types of hydrocarbons such as saturated hydrocarbons. However,this will generally decrease the heat produced by the combustionreaction so as to possibly require a supplemental heat source (i.e.electric, plasma, microwave, combustion zones exterior to the reactorchamber but in heat exchange relationship with the reactor chamber,etc.) to obtain the desired temperature conditions in the reaction zone.In any event it is preferable that the hot combustion products asproduced by combustion in the combustion zone provide at least about 15%of the energy needed to maintain desired temperature conditions of atleast about 1400° C. in the reaction zone.

EXAMPLES

Specific examples will now be described to further illustrate theinvention. These examples should not be construed to limit the inventionin any manner.

In each of the following examples, various gaseous flow rates are givenin gram moles/minute (abbreviated to gmol/min hereafter). Actualmeasurements of flow rate were taken volumetrically at room temperatureand atmospheric pressure in units of liters/minute. These volumetricmeasurements were converted to gmol/min by assuming there are 24.45liters/mole for any gas at 25° C. (room temperature) and at atmosphericpressure. All flow rates for gases below are undiluted with any othergases (i.e. carrier gases).

With respect to elemental analysis results given in various tables, thecarbon weight percentages were obtained by means of CHNS combustionanalysis, silicon percentages by X-ray fluorescence analysis, and theoxygen percentages by neutron activation analysis. In each example wherean elemental analysis was performed, CHNS analysis revealed detectableamounts of hydrogen. However, such detected amounts of hydrogen wereless than 1 weight percent and are not reported in the followingexamples. Weight percentage results which are provided have not beennormalized to 100%. Variance from 100% is attributable to normalanalysis inaccuracies.

Deposits on the reactor chamber walls were mentioned in several runshereafter described. Such deposits were not measured quantitatively, butvisual observations were made after the completion of various runs.These observations are given in subsequent examples in terms of "light","medium" and "heavy" to reflect the comparability of deposits obtainedfor the various runs.

With respect to terminology and notations used hereafter, it will beunderstood that all degree readings obtained by X-ray diffraction arefor an angle of 2θ.

EXAMPLE I

The purpose of this example is to demonstrate the formation of siliconcarbide with a reactor substantially similar to that shown in FIGS. 1-4.

The reactor of this example utilized a Dacron® filter bag to collectproduct powder exiting from a quartz conduit having one end incommunication with the downstream end of the reactor. Important reactordimensions are given in Table IA.

                  TABLE IA                                                        ______________________________________                                        Item                 Dimension                                                ______________________________________                                        Diameter of Chamber 12                                                                              5.08 cm                                                 Overall Length of Chamber 12                                                                        50.8 cm                                                 Length of Combustion Zone 12a                                                                       22.9 cm                                                 Length of Reaction Zone 12b                                                                         27.9 cm                                                 Overall O.D. of Reactor 10                                                                          37.5 cm                                                 O.D. of Tubular Member 62                                                                          0.953 cm                                                 I.D. of Tubular Member 62                                                                          0.216 cm                                                 O.D. of Tubular Member 74                                                                          0.318 cm                                                 I.D. of Tubular Member 74                                                                          0.236 cm                                                 O.D. of Tubular Member 76                                                                          0.953 cm                                                 I.D. of Tubular Member 76                                                                          0.396 cm                                                 ______________________________________                                    

Using the above described apparatus, three runs were made using amixture of ethylene and acetylene as the fuel and pure oxygen as theoxidant. Flow rates for the ethylene, acetylene and oxygen in each ofthe runs were 1.28 gmol/min, 0.33 gmol/min and 1.57 gmol/min,respectively, wherein gmol/min. represents gram moles/minute.Accordingly, the elemental ratio of carbon to oxygen for the combustiblemixture only (combustion C:O ratio) was 1.02. Table IB summarizes otherdata for runs 1-3, wherein silane (SiH₄) and propylene (C₃ H₆) wereemployed as reactants at different flow rates. Table IB also indicatesthe flow rate of helium (He) purge gas through the reactant nozzle, theelemental molar ratio of carbon to oxygen for the combination of thereactants and combustible mixture (overall C:O ratio), the synthesisrate, the run time, product mass collected, the mass ratio, and resultsof product elemental analysis.

The "product mass" collected is the mass of raw product actuallycollected in the filter bag at the completion of each run. The terms"synthesis rate" and "mass ratio" have been previously defined. Indetermining the synthesis rate, the molecular weight of silicon carbide(SiC) is assumed to be about 40 g/gmol and the molar flow rate ofsilicon atoms into the reaction zone is equivalent to the flow rate ofSiH₄ indicated in Table IB. In determining mass ratio, the molar flowrates of fuel and oxygen in Table IB are converted to mass flow units ofg/min.

                                      TABLE IB                                    __________________________________________________________________________                                                   Product Analysis               Run                                                                              SiH.sub.4                                                                           C.sub.3 H.sub.6                                                                     He    Overall                                                                             Syn. Rate                                                                           Time                                                                             Product Mass                                                                         Mass                                                                              Wt. % Composition              No.                                                                              gmol/min                                                                            gmol/min                                                                            gmol/min                                                                            C:O Ratio                                                                           g/min mins.                                                                            g      Ratio                                                                             Si C   O                       __________________________________________________________________________    1  0.068 0.108 0.157 1.13  2.7   30 61.5   0.029                                                                             63.4                                                                             24.5                                                                              9.2                     2  0.137 0.227 0.314 1.24  5.5   15 66.9   0.058                                                                             64.5                                                                             24.3                                                                              8.5                     3  0.269 0.459 0.628 1.46  10.8  15 79.3   0.114                                                                             61.7                                                                             26.1                                                                              9.2                     __________________________________________________________________________

It can be seen from Table IB that the elemental composition issubstantially unaffected by increasing the synthesis rate (at a constantflow of combustible mixture) and consequently also the mass ratio.

Powder X-ray diffraction patterns obtained for products resulting fromruns 1 and 2 exhibit distinct peaks at 35°, 60° and 72°, indicating thepresence of beta silicon carbide. The pattern corresponding to theproduct from run 3 shows a distinct peak at 35° and only a broad, poorlydefined peak at about 60°, thereby indicating a decrease incrystallinity in response to an increase in synthesis rate and massratio.

The product from run 1 was further analyzed with respect to particlesize in accordance with the following procedure. A small portion, on theorder of milligrams, of the product powder was placed in a beakercontaining 40 cc of a mixture of 0.07 weight percent Triton dispersant(Rohm & Haas Co., Philadelphia, Pa.) and distilled water. The resultingsolution was ultrasonically treated for 10 minutes at a power level of40 watts using a Model W-380 ultrasonic horn (Heat Systems UltrasonicsInc., Farmingdale, N.Y.). A particle size distribution was measuredusing a CAPA-700 Particle Analyzer (Horiba, Tokyo, Japan). The resultingparticle size distribution indicates particle diameters ranging fromless than about 0.04 micron to about 0.2 micron, with the largestpercentage (about 32%) of particles examined falling in the particlediameter range of 0.10 to 0.20 micron.

Deposits on the reactor chamber wall were observed after the completionof each of runs 1-3, and were found to be as follows: run 1-no deposits;run 2-light deposits on upper 3 inches of chamber wall; run 3-heavyheavy deposits on upper 5 inches of chamber wall.

EXAMPLE II

The purpose of this example is to demonstrate the production of siliconcarbide using different fuels in conjunction with a reactor inaccordance with the design illustrated in FIGS. 1-4.

The dimensions of the reactor of this example were substantiallyidentical to the dimensions of the reactor described in Example I, withthe exception of the combustion nozzles. Tubular member 62 of eachcombustion nozzle had an I.D. of 0.257 cm in run 4 and an I.D. of 0.334in run 5.

Run 4 utilized a mixture of acetylene (C₂ H₂) and ethylene (C₂ H₄)whereas run 5 utilized only ethylene as a fuel. Each of these runsemployed silane at a flow rate of 0.269 gmol/min, giving a synthesisrate of 10.8 g/min, and propylene at a flow rate of 0.459 gmol/minthrough the reactant nozzle. Further process data is summarized in TableIIA and product analysis data is set forth in Table IIB.

                                      TABLE IIA                                   __________________________________________________________________________    Run                                                                              He    C.sub.2 H.sub.4                                                                     C.sub.2 H.sub.2                                                                     O.sub.2                                                                             Comb. Overall                                                                             Time                                                                             Product Mass                                                                         Mass                         No.                                                                              gmol/min                                                                            gmol/min                                                                            gmol/min                                                                            gmol/min                                                                            C:O Ratio                                                                           C:O Ratio                                                                           mins.                                                                            g      Ratio                        __________________________________________________________________________    4  --    1.87  0.46  2.21  1.05  1.36  7  58.6   0.080                        5  0.628 3.79  --    3.71  1.02  1.21  7.5                                                                              55.4   0.048                        __________________________________________________________________________

                  TABLE IIB                                                       ______________________________________                                        Product Analysis                                                              Wt. % Composition                                                             Run      Si            C      O                                               ______________________________________                                        4        64.1          30.9   6.9                                             5        61.2          23.4   16.1                                            ______________________________________                                    

It can be seen from the above data that the product from run 5, whichused only ethylene as the fuel, had a substantially higher oxygencontent than the product from run 4, which used a mixture of ethyleneand acetylene. These results were obtained despite the fact that run 5employed higher fuel and oxygen flow rates than run 4.

Powder X-ray diffraction patterns for the products from runs 4 and 5exhibit distinct peaks at 35°, 60° and 72°, clearly indicative of thepresence of beta silicon carbide.

Deposits observed at the completion of each of runs 4 and 5 weresubstantially similar; that is, light deposits on the upper 3 inches ofthe reactor chamber wall.

EXAMPLE III

This example is an additional demonstration of the production of siliconcarbide using the reactor of FIGS. 1-4. This example further provides atemperature measurement in the reaction zone which was made duringsilicon carbide production.

Dimensions of the reactor of this example were substantially identicalto those cited for the reactor of Example I, with the exception of theI.D. of tubular member 62, which was 0.257 cm.

The run of this example, hereafter denoted as run 6, employed thefollowing process conditions: reactants silane and propylene at flowrates of 0.137 gmol/min and 0.227 gmol/min respectively; helium purgegas flow rate of 0.314 gmol/min; fuel flow rates of ethylene andacetylene of 1.56 gmol/min and 0.65 gmol/min respectively; oxygen flowrate of 2.21 gmol/min; combustion C:O ratio of 1.00; overall C:O ratioof 1.15; synthesis rate of 5.5 g/min; run time of 7 mins; product masscollected of 26 g; mass ratio of 0.042.

The reaction zone temperature was measured as 1552° C. along the reactorchamber axis and 12.7 cm upstream from the downstream end of thechamber. A thermocouple comprising bare wires of different compositionswere employed to make this measurement. One wire was composed of 100%iridium whereas the other wire was composed of 60% iridium and 40%rhodium. The two wires were run through a two hole electrical insulatormade of 99.8% alumina, and the insulator and wires were encased in a0.79 cm O.D. closed end 99.8% alumina tube to protect the wires fromattack by the silicon reactant. A thermocouple junction was formed byextending the wires about 0.5 cm beyond the alumina tube and spotwelding the wires together. This junction was located on thelongitudinal axis of the reactor chamber. Since the reactor walls areinsulated and hence operate close to the same temperature as the gasesin the chamber, the thermocouple readings were not corrected forradiation error.

Product analysis revealed the following weight percentages with respectto the raw product collected from run 6: 64.5 weight percent Si; 30.5weight percent C; and 4.6 weight percent O.

The powder X-ray diffraction pattern for the raw product from run 6revealed prominent, distinct peaks at 35°, 60° and 72°, clearlyindicative of the presence of beta silicon carbide.

EXAMPLE IV

The purpose of this example is to demonstrate the sintering of a ceramicpart from a purified product, wherein the purified product is derivedfrom the raw product as produced by a reactor in accordance with thedesign of FIGS. 1-4.

The reactor of this example was substantially identical to the reactorof Example III.

The reactor run of this example, hereafter denoted as run 7, employedthe following process conditions: fuel flow rates of ethylene andacetylene of 1.85 gmol/min and 0.45 gmol/min respectively; oxygen flowrate of 2.21 gmol/min; combustion C:O ratio of 1.04; reactant flow ratesof silane and propylene of 0.137 gmol/min and 0.227 gmol/minrespectively; helium purge gas flow rate of 0.314 gmol/min; overall C:Oratio of 1.19; synthesis rate of 5.5 g/min; run time of 270 mins.;product mass collected of 1633 g; and mass ratio of 0.041.

Product analysis of the collected raw product powder revealed thefollowing weight percentages: 60.4 weight percent Si; 29.2 weightpercent C; and 11.4 weight percent O. Powder X-ray diffraction analysisof the raw product revealed peaks at 35°, 60° and 72°, indicative of thepresence of beta silicon carbide.

A portion of the raw product was purified, or processed, as follows. 875grams of the raw product was mixed with 52 grams of carbon black (BlackPearls 2000, Cabot Corp.). The resulting mixture was placed in agraphite box, and the box was placed in a controlled atmosphere furnacepurged with argon. The furnace was heated to 1550° C. at 25° C./min andheld at 1550° C. for 2.5 hours. The resulting powder was oxidized in airat 600° C. to remove free carbon. The purified powder was subjected toelemental analysis and was found to contain 69.4 weight percent Si, 28.6weight percent C and 1.4 weight percent O.

The purified product was sintered using boron and carbon sintering aids.110 grams of the purified product mixed with 1.375 grams of elementalboron powder (Callery Chemical), 4.4 grams of OLOA 1200 dispersant(Chevron Chemical), 4.4 grams of stearic acid (Fisher Scientific), and10.66 grams of phenolic resin (Durez 14000, Occidental) was milled for24 hours in a heptane/ethanol mixture using nylon-coated steel balls.After milling, the solvent was evaporated and the dried cake was crushedand sieved (US standard sieve #40). The resulting powder was uniaxiallypressed at 4000 psi into discs 4.4 cm in diameter and 0.3 cm thick. Thediscs were isostatically pressed at 50,000 psi to approximately 3.9 cmin diameter and 0.27 cm thick. The discs were sintered individually in acontrolled atmosphere furnace employing the following sequence of steps:(1) evacuate furnace to 200 millitorr; (2) heat to 1000° C. at a rate of65° C./minute; (3) heat to 1550° C. at a rate of 40° /minute; (4) raisefurnace pressure to 300 millitorr with argon; (5) heat to 2100° C. at arate of 40° C./minute, and hold at 2100° C. for 60 minutes; and (6)allow furnace to cool to room temperature. Twenty discs were sinteredusing the above procedure.

Individual densities of the twenty discs were determined and averaged togive an average density of 3.00 g/cc, or 93% of "theoretical density",the density of pure crystalline silicon carbide.

EXAMPLE V

The purpose of this example is to demonstrate the production of siliconcarbide using a reactor similar to that shown in FIGS. 5-7.

Dimensions of the reactor of this example were substantially the same asthose cited for the reactor of Example I, with the exception of the I.D.of tubular member 176a, which was 0.333 cm. Of course, the embodiment ofthe reactant nozzle of FIG. 7 does not include a tubular memberanalogous to tubular member 74.

Three runs were made at different synthesis rates. Run 8 used only onereactant nozzle whose outlet was positioned on the reactor chamber axis.Runs 9 and 10 used two and four reactant nozzles, respectively. Suchnozzles were symmetrically spaced around the chamber axis such thattheir tips contacted one another. The additional reactant nozzles wereneeded to accommodate the increased total reactant flows. It was foundthat reactant flow rate through an individual reactant nozzle inaccordance with the design of FIG. 7 had to be limited to a relativelylow flow rate to avoid a disrupted flow pattern resulting from reactantflow through the L-shaped passage in the tip.

Flow rates for the combustible mixture in each run were as follows:ethylene at 1.26 gmol/min, acetylene at 0.32 gmol/min, oxygen at 1.57gmol/min, and a combustion C:O ratio of 1.01.

Additional data is summarized in Table V. The reactant flow rate asgiven for each of runs 9 and 10 is the total flow rate from the reactantnozzles.

                                      TABLE V                                     __________________________________________________________________________                                             Product Analysis                     Run                                                                              SiH.sub.4                                                                           C.sub.3 H.sub.5                                                                     Overall                                                                             Syn. Rate                                                                           Time                                                                             Product Mass                                                                         Mass                                                                              Wt. % Composition                    No.                                                                              gmol/min                                                                            gmol/min                                                                            C:O Ratio                                                                           g/min mins.                                                                            g      Ratio                                                                             Si C   O                             __________________________________________________________________________    8  0.137 0.227 1.22  5.5   20 73     0.059                                                                             65.2                                                                             32.0                                                                              3.5                           9  0.269 0.459 1.45  10.8  10 82.3   0.115                                                                             68.3                                                                             29.7                                                                              2.6                           10 0.553 0.928 1.89  22.1   5 90.0   0.236                                                                             65.7                                                                             27.7                                                                              5.0                           __________________________________________________________________________

It can be seen from Table V that the elemental composition of theproduct does not change dramatically with an increase in synthesis rateand mass ratio.

The powder X-ray diffraction pattern for the product from run 8 exhibitsdistinct peaks at 35°, 60° and 72°, indicative of the presence of betasilicon carbide. The X-ray diffraction pattern for the product from run9 shows a distinct peak at 35°, but only broad, poorly defined peaks at60° and 72°. The X-ray diffraction pattern for the product from run 10shows a peak at 35°, but only a barely perceptible, broad shoulder atabout 60°. This data shows in a similar manner to the data of Example Ia decrease in crystallinity with increasing synthesis rate and massratio.

Observed deposits after the completion of each of runs 8-10 were asfollows: run 8--medium deposits; run 9--medium deposits with smallbuild-up on reactant nozzles; and run 10--heavy deposits with largebuild-up on reactant nozzles. In each run, observed deposits extendedalong the entire length of the reaction zone.

THAT WHICH IS CLAIMED IS:
 1. A method comprising the steps of:providinga reactor having a chamber defined therein which has a longitudinal axisand longitudinally separated upstream and downstream ends, wherein thechamber comprises a combustion zone and a reaction zone such that thecombustion zone longitudinally extends from said upstream end to asurface boundary between the zones and such that the reaction zonelongitudinally extends from said surface boundary to said downstreamend; establishing a flow of a combustible mixture in the combustion zoneso as to generally flow in a direction generally toward the reactionzone, wherein the combustible mixture comprises a mixture of a fuel andan oxidant; combusting the combustibel mixture in the combustion zone toproduce hot combustion products which flow generally toward and into thereaction zone; injecting at least one reactant into the chamber from atleast one outlet of at least one reactant nozzle such that said at leastone reactant exits said at least one reactant nozzle outlet at saidsurface boundary in a direction generally parallel to said longitudinalaxis, wherein temperature conditions in at least a portion of thereaction zone are at least about 1400° C. and wherein the elementalmolar ratio of carbon to oxygen for the combination of the combustiblemixture and said at least one reactant is at least about 0.8:1, said atleast one reactant being capable of reacting in the reaction zone toform a carbide compound; whereby a product powder comprising the carbidecompound is produced in the reaction zone.
 2. A method as recited inclaim 1 wherein the flow of combustible mixture is established in thecombustion zone by injecting the combustible mixture into the combustionzone from at least one outlet of at least one combustion nozzle, said atleast one combustion nozzle outlet defining at least one linear boundarywhose projection in a direction generally parallel to said longitudinalaxis and onto said surface boundary generally surrounds said at leastone reaction nozzle outlet.
 3. A method as recited in claim 2 whereinsaid at least one reaction nozzle outlet comprises a single reactionnozzle outlet positioned substantially on said longitudinal axis suchthat said at least one reactant exits said at least one reactant nozzleoutlet generally along said longitudinal axis and toward said downstreamend.
 4. A method as recited in claim 3 wherein said reaction nozzleoutlet is positioned so as to be generally centrally located within saidprojection of said at least one linear boundary.
 5. A method as recitedin claim 4 wherein said at least one combustion nozzle comprises aplurality of combustion nozzles, each combustion nozzle having acorresponding outlet.
 6. A method as recited in claim 5 wherein saidplurality of combustion nozzle outlets are equidistantly spaced from oneanother.
 7. A method as recited in claim 6 wherein said plurality ofcombustion nozzle outlets are positioned to define a generallytriangular linear boundary.
 8. A method as recited in claim 7 whereinsaid plurality of combustion nozzle outlets are positioned closelyadjacent to said upstream end.
 9. A method as recited in claim 1 whereinsaid elemental molar ratio is in the range of about 0.9:1 to about1.5:1.
 10. A method as recited in claim 9 wherein said elemental molarratio is in the range of about 1:1 to about 1.3:1.
 11. A method asrecited in claim 10 wherein the elemental molar ratio for thecombustible mixture is at least about 0.7:1.
 12. A method as recited inclaim 11 wherein the elemental molar ratio for the combustible mixtureis in the range of about 0.9:1 to about 1.1:1.
 13. A method as recitedin claim 12 wherein said temperature conditions are in the range ofabout 1400° C. to about 1700° C.
 14. A method as recited in claim 1wherein the fuel comprises a hydrocarbon selected from the groupconsisting of ethylene, propylene, butene, propadiene, butadiene,propyne, butyne, and mixtures thereof.
 15. A method as recited in claim14 wherein the fuel comprises a mixture of ethylene and acetylene.
 16. Amethod as recited in claim 1 wherein said at least one reactantcomprises a first reactant, which includes a first component, and also asecond reactant containing a second, carbon component, wherein saidfirst and second reactants react to form said carbide compound, saidcarbide compound being a compound of said first component and saidsecond, carbon component.
 17. A method as recited in claim 16 whereinsaid first component is selected from the group consisting of silicon,boron, tungsten, chromium, titanium, zirconium, molybdenum, and iron.18. A method as recited in claim 17 wherein said first component issilicon.
 19. A method as recited in claim 18 wherein said first reactantis silane.
 20. A method as recited in claim 16 wherein said secondreactant comprises a C₁ -C₉ carbon compound.
 21. A method as recited inclaim 20 wherein said C₁ -C₉ carbon compound is a hydrocarbon selectedfrom the group consisting of methane, ethane, propane, butane, pentane,hexane, heptane, octane, nonane, ethlyene, propylene, acetylene,benzene, toluene, cyclopropane, cyclobutane, cyclopentane, cyclohexane,and mixtures thereof.
 22. A method as recited in claim 16 wherein a massratio is provided of no more than about 0.3.
 23. A method as recited inclaim 3 wherein said at least one reactant comprises a first reactant,which includes a first component, and also a second reactant containinga second, carbon component, wherein said first and second reactantsreact to form said carbide compound which is a compound of said firstcomponent and said second, carbon component, and wherein both said firstand second reactants are injected into the chamber from said singlereaction nozzle outlet.
 24. A method comprising the steps of:providing areactor having a chamber defined therein which has a longitudinal axisand longitudinally separated upstream and downstream ends, wherein thechamber comprises a combustion zone and a reaction zone such that thecombustion zone longitudinally extends from said upstream end to asurface boundary between the zones and such that the reaction zonelongitudinally extends from said surface boundary to said downstreamend; establishing a flow of a combustible mixture in the combustion zoneso as to flow in a direction generally toward the reaction zone, whereinthe combustible mixture comprises a mixture of a fuel and an oxidantcomprising oxygen: combusting the combustible mixture in the combustionzone to produce hot combustion products which flow generally toward andinto the reaction zone; injecting at least one reactant into the chamberfrom at least one outlet of at least one reactant nozzle such that saidat least one reactant exits said at least one reactant nozzle outlet atsaid surface boundary in a direction generally parallel to saidlongitudinal axis, wherein temperature conditions in at least a portionof the reaction zone are at least about 1400° C. and wherein theelemental molar ratio of carbon to oxygen for the combination of thecombustible mixture and said at least one reactant is at least about0.8:1, said at least one reactant being capable of reacting in thereaction zone to form a carbide compound; whereby a product powdercomprising the carbide compound is produced in the reaction zone.
 25. Amethod comprising the steps of:providing a reactor having a chamberdefined therein which has a longitudinal axis and longitudinallyseparated upstream and downstream ends, wherein the chamber comprises acombustion zone and a reaction zone such that the combustion zonelongitudinally extends from said upstream end to a surface boundarybetween the zones and such that the reaction zone longitudinally extendsfrom said surface boundary to said downstream end; establishing a flowof a combustible mixture in the combustion zone so as to generally flowin a direction generally toward the reaction zone, wherein thecombustible mixture comprises a mixture of a fuel and an oxidant;combusting the combustible mixture in the combustion zone to produce hotcombustion products which flow generally toward and into the reactionzone; injecting at least one reactant into the chamber from at least oneoutlet of at least one reactant nozzle such that said at least onereactant is substantially gaseous as injected into said chamber and suchthat said at least one reactant exits said at least one reactant nozzleoutlet at said surface boundary in a direction generally parallel tosaid longitudinal axis, wherein temperature conditions in at least aportion of the reaction zone are at least about 1400° C. and wherein theelemental molar ratio of carbon to oxygen for the combination of thecombustible mixture and said at least one reactant is at least about0.8:1, said at least one reactant being capable of reacting in thereaction zone to form a carbide compound; whereby a product powdercomprising the carbide compound is produced in the reaction zone.